Alkylene polyamines such as ethylenediamine are used in a wide variety of applications. For example, ethylenediamine has wide utility and is used in the manufacture of chelating agents, surfactants, fabric softeners, lubricating oil additives, rubber accelerators, fungicides, insecticides, synthetic waxes, asphalt wetting agents and resinous polymers.
Highly acidic catalysts such as reductive metal catalysts have been employed in the production of alkyleneamines. However, such acidic catalysts are often non-selective for alcohol/amine reactions yielding a product mixture which also contains the corresponding ether, unsaturated hydrocarbon, polymeric hydrocarbon and other by-products.
Certain acidic phosphorus-containing catalysts are known to agglomerate and leach from the catalyst under standard liquid phase reaction conditions. Moreover, the use of reductive metal catalysts is not entirely satisfactory because the reaction involves high pressures, often greater than 1500 psi, and large molar ratios, typically greater than 5:1 of ammonia to alkanolamine. Consequently, a need exists to develop highly active and/or selective catalysts for producing alkylene polyamines, including polyalkylene polyamines.
British Patent 1,508,460 discloses a process for making diethylene triamine and/or triethylenetetramine by disproportionation of ethylenediamine. The conversion of ethylenediamine is carried out over a catalyst containing at least one transition metal selected from Group 8 of the Periodic Table of the Elements. The reaction is conducted at temperatures ranging from about 100.degree. to 150.degree. C. in the presence of hydrogen gas. The reaction is taken to a degree of conversion of 70% or less and does not form form linear products larger than triethylenetetramine.
U.S. Pat. No. 4,036,881 discloses a process for selectively preparing predominantly noncyclic polyalkylene polyamines wherein an alkylenediamine is contacted with an alkanolamine in the presence of a catalytically effective amount of a phosphorus-containing substance at a temperature of 250.degree. C. to about 350.degree. C. under a pressure sufficient to maintain the mixture essentially in the liquid phase. Suitable phosphorus-containing substances include acidic metal phosphates, phosphoric acid compounds and their anhydrides, phosphorous acid compounds and their anhydrides and the like.
U.S. Pat. No. 4,313,003 discloses a process for disproportionating monomethylamine to dimethylamine and ammonia wherein monomethylamine is passed over various catalysts including mordenite wherein the primary cation is Na, HNa having at least 2% Na, Mg, Ca, Ba at a temperature of 250.degree. to 475.degree. C. and a pressure of 7 to 7,000 kPa at a feed rate of 0.1 to 10 g of monomethylamine/g catalyst per hour, at a monomethylamine conversion of 15 to 75%.
U.S. Pat. No. 4,394,524 discloses a process for preparing noncyclic polyalkylene polyamines wherein ammonia, an alkylene polyamine and an alkanolamine are reacted in the presence of an effective amount of a phosphorus-containing substance or a salt of a sulfur-containing substance or its corresponding acid. The reaction is conducted at a temperature from about 200.degree. to 350.degree. C. under a pressure sufficient to maintain the reaction mixture essentially in the liquid phase. Suitable phosphorus-containing materials are enumerated in U.S. Pat. No. 4,036,881, which is discussed herein.
U.S. Pat. No. 4,503,253 discloses a process for preparing predominantly noncyclic polyalkylene polyamines wherein (1) an alkanolamine and (2) either ammonia, an alkyleneamine, or a primary or secondary amine are reacted in the presence of a catalyst. Suitable catalysts include phosphoric acid which is incorporated onto an inert support. The reaction is conducted at a temperature from about 175.degree. to 400.degree. C. under a pressure sufficient to maintain a substantial amount of the ammonia or amine in the reaction zone. Inert supports which can be utilized include silica, alumina carbon silica-alumina clays and molecular sieves such as aluminosilicates.
U.S. Pat. No. 4,547,591 discloses a process for preparing predominantly linear polyethylenepolyamines wherein ethylenediamine and an alkanolamine are reacted at a temperature ranging from 250.degree. C. to about 400.degree. C. and a pressure ranging from 500 to about 5000 psig in the presence of about 0.01 to about 20.0 weight percent of a silica-alumina catalyst and about 0.1 to about 3.0 weight percent of a phosphorus acid co-catalyst.
U.S. Pat. No. 4,578,517 discloses a process for preparing polyalkylene polyamines wherein ammonia or a primary or secondary amine and an alkanolamine compound are reacted in the presence of an effective amount of a Group IIIB metal acid phosphate at a temperature from about 175.degree. to 400.degree. C. under a pressure sufficient to maintain a substantial amount of the ammonia or amine in the reaction zone.